Triazole compounds, their intermediates, and method for production of the same

ABSTRACT

The present invention relates to a triazole compound represented by the formula (1): ##STR1## wherein R 1  represents a lower alkyl group which may have a substituent; R 2  and R 3  represent respectively hydrogen, an aryl group, a benzoyl group, a tosyl group, a lower alkoxy carbonyl group, or an aryl sulfonyl group, each of which except for hydrogen may have a substituent; provided that when R 2  is hydrogen, the triazole compound is represented by the formula (2): ##STR2## wherein R 1  and R 3  have the same as defined above.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel triazole compounds, theirintermediates, and a method for the production of the same.

2. Description of the Prior Art

Compounds having an isocyanate group, because of their excellentreactivity, have been widely used in the area of polymer chemistry. Inparticular, compounds having both a polymerizable carbon-carbonunsaturated group and an isocyanate group in same molecule can be usedin a wide range of industrial areas because those functional groups willparticipate in various reactions under different reaction mechanisms.For good utilization of such useful features, the present inventorspreviously proposed an acyl isocyanate compound expressed by thefollowing formula: ##STR3## where, R₁ represents a lower alkyl groupwhich may have a substituent (Japanese Patent Application Sho58-225226).

The acyl isocyanate compound (5) is generally in the; form of a liquidstable at ordinary temperatures and is easy to handle. The compound hasa polymerizable carbon-carbon unsaturated group and an isocyanate groupin its molecules and, in addition, it has a carbonyl group presentbetween those two functional groups and in proximity thereto, so thatnot only is the activity of the carbon-carbon unsaturated groupenhanced, but the activity of the isocyanate group is also enhanced andso that the compound is ready to perform a variety of additionreactions.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a novel compoundderived from an alkyl acryloyl isocyanate represented by the followingstructural formula (5): ##STR4## (wherein R₁ represents a lower alkylgroup which may have a substituent group), in which the acyl isocyanategroup is converted into a triazole group, with the carbon-carbonunsaturated group being retained as it is.

More specifically, the invention relates to a triazole compoundrepresented by the formula (1): ##STR5## wherein R¹ represents a loweralkyl group which may have a substituent; R² and R³ representrespectively hydrogen, an aryl group, a benzoyl group, a tosyl group, alower alkoxy carbonyl group, or an aryl sulfonyl group, each of whichexcept for hydrogen may have a substituent; provided that when R². ishydrogen, the triazole compound is represented by the formula (2):##STR6## wherein R¹ and R³ have the same as defined above.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to a triazole compound represented by the formula(1): ##STR7##

In the formula (1), R¹ represents a lower alkyl group, which may have asubstituent. Specifically, it is an alkyl group having a carbon numberof 1 to 6, such as a methyl group, an ethyl group, a butyl group, or ahexyl group.

R² and R³ represent respectively hydrogen, or an aryl group, a benzoylgroup, a tosyl group, a lower alkoxy carbonyl group, or an aryl sulfonylgroup. Each group (except for hydrogen) represented as R² or R³ may havea substituent. The aryl group is specifically one having a carbon numberof 6 to 20, such as phenyl and naphthyl. The alkoxy group of the alkoxycarbonyl group has a carbon number of 1 to 8 Examples of aryl sulfonylgroup are specifically phenyl sulfonyl and toluene sulfonyl (includingo-, m-, p-).

The substituent which may be bonded to the group represented as R² or R³is exemplified by methyl, ethyl, propylbutyl, 2-ethyl hexyl,methoxyethyl, ethoxyethyl, butoxyethyl, hexyloxyethyl, methoxy, nitro,chloro, and bromo.

In the formula (1), when R² is hydrogen, the compound is a triazolecompound expressed by the formula (2): ##STR8## in which R¹ and R³ arethe same as above noted.

A triazole compound of the invention expressed by the; formula (1) canbe easily produced by heating a hydrazide compound expressed by thefollowing formula (3): ##STR9## in which R₁, R₂ and R₃ are the same asabove mentioned. The hydrazide compound (3) can be easily obtained bycarrying out a reaction between an acyl isocyanate compound representedby the formula (5): ##STR10## in which R₁ is the same as above mentionedand a hydrazine compound (6): ##STR11## in which R₂ and R₃ are the sameas above mentioned. It is considered that this reaction will proceedunder ring formation and dehydration as illustrated: ##STR12##

Where R² is hydrogen, a compound expressed by the formula (2) isproduced by tautomerism as follows: ##STR13##

The reaction is carried out between the compound (5)

and the hydrazine compound (6) of 1 to 5 equivalents in an inactivesolvent at a suitable temperature within the range of -2 to 200° C.Then, an after-treatment according to a conventional method, such asconcentration, and a purifying operation, such as recrystallization orcolumn chromatography, are carried out to give a hydrazide compound (3).Generally, the compound (3) is solid and, therefore, recrystallizationis most suitable for the compound (3).

Further heating of the hydrazide compound (3) will give the triazolecompound (1). The compound (3) is also a novel compound.

The heating reaction above is usually carried out in an inactive solventor an aqueous solution of potassium hydroxide. Inactive solvents usefulfor the purpose of the invention include, for example, aliphatichydrocarbons, such as pentane and hexane; aromatic hydrocarbons, such asbenzene, toluene, and xylene; alicyclic hydrocarbons, such ascyclohexane and cyclopentane; halogenated hydrocarbons, such aschloroform, dichloromethane, dichlorobenzene, and bromobenzene; ketones,such as acetone, methylethyl ketone, and cyclohexanone; esters, such asethyl acetate and butyl acetate; ethers, such as diethylether, THF,dioxane, diisopropyl ether, anisole, and diphenyl ether; nitriles, suchas acetonitrile and benzonitrile; amides, such as dimethylformamide andN-methylpyrrolidone; nitrobenzene; and dimethylsulfoxide. These inactivesolvents may be suitably selected in consideration of heatingtemperature, solubility and other factors. Dehydrating agents, such asmagnesium sulfide, sodium sulfide and molecular sieves, may be added tothe system as required. Heating reaction is carried out at a suitabletemperature within the range of room temperature to 200° C.Subsequently, concentration is effected as required, followed bypurifying, to obtain a triazole compound (1) of the present invention.For purifying purposes, recrystallization is most suitable since thecompound (1) is usually solid, but other conventional purifying methods,including column chromatography, may be employed.

The triazole compound (1) of the present invention, where R³ is ahydrogen atom, can also be obtained by hydrolyzing the followinghydrazone compound (4): ##STR14## in which R¹ R² are the same as definedin the formula (1) R⁴ and R⁵ represent a lower alkyl group or an arylgroup and, more specifically, include groups identical with thoseenumerated with respect to the previously described R² and R³. Thehydrazone compound (4) can be easily obtained by causing the acylisocyanate (5) to react with the hydrazone compound expressed by theformula (7): ##STR15## in which R², R⁴, and R⁵ are the same as earlierdefined. This reaction is carried out under practically the samereaction conditions as those described earlier for the reaction betweenacyl isocyanate compound (5) and hydrazine compound (6).

The hydrazone compound (4) obtained is hydrolyzed to produce thetriazole compound (1). This reaction is carried out, for example, underreflux with heating in a 10% aqueous solution of acetic acid for about30 minutes.

This process of reaction for production of the triazole compound fromthe hydrazone is shown below by chemical formulas: ##STR16##

In accordance with the invention it is possible to produce the noveltriazole compound (1) and intermediate compounds thereof. These newcompounds are generally stable and has good storage stability and, inaddition, they are in solid state, so that they are easy to purify andhandle. Furthermore, these new compounds (1), (3) and (4) have variousactive structures and/or active groups A to C; therefore, they canparticipate in various reactions and accordingly can be used in a widerange of applications. ##STR17##

For example, in the above formulas, the structure A, which is aconjugate double bond structure, has polymerization reactivity and,therefore, the foregoing compounds (1), (3), and (4) can be used inproducing homopolymers and copolymers. For example, these compounds maybe graft-polymerized for use in modifying synthetic fibers, syntheticresins, natural polymers and the like. Also, they may be polymerized perse or with any other comonomer for use in producing varnishes, paints,adhesives, plastics, elastomers, etc.

The structure B, which is an acyl urethane structure or a semicarbazidebond, has high intermolecular cohesive force and high intermolecularhydrogen bond forming ability. Therefore, polymers obtained by usingcompounds (1), (2) and (3) can be expected to exhibit excellentperformance characteristics in respect of toughness, adhesiveness anddispersibility.

The structure C, which is an amino group containing structure, is basicand can be used as a pendant for functional groups or in cross-linkingof functional groups. In addition, it has high reactivity and canexhibit strong cationic characteristics when chlorinated orquaternarized. Therefore, reaction products obtained through the use ofcompounds (1), (3) and (4) have good water solubility and/or hydrophilicnature, good dyeability with acid dyes, and good reactivity and/oradsorptivity relative to anions. Further, such products exhibit goodcohesiveness relative to negative colloids, such as sewage sludge andcellulose, have good electrical characteristics, such aselectrifiability and conductivity, and also have good adhesion anddispersion properties.

In this way, the compounds (1), (3) and (4), as industrial rawmaterials, are useful in a wide range of applications.

It is noted that the isocyanate compound (5), as the starting material,can be produced by causing α-alkyl acryl amide with oxalyl halide.

EXAMPLES

To illustrate the invention in further detail, the following examplesare given. It is understood, however, that the invention is not limitedby any of these examples.

Example 1

To a THF solution (3 ml) of phenylhydrazine (1.5 g, 13.9 mmol) was addeddropwise a THF solution (3 ml) of methacryloyl isocyanate (1.69 g, 15.0mmol) at -10° C. in 40 minutes. Then, agitation was carried out at thesame temperature for one hour. The precipitate was filtered to give 1.41g of a white solid semicarbazide material. The flitrate was concentratedunder reduced pressure, and the residue was recrystallized from benzene,with the result that 0.94 g of a colorless needle-like crystallinesemicarbazide material was obtained. The yield was 77%. The material hada melting point of 184 to 185° C.

IR (KBr) 3294, 3228 (NH), 1678 cm⁻¹ (C =0).

¹ H NMR (CDCl₃) δ=1.92 (3H, d, J =1.5 Hz, CH₃), 5.40 (1H, q, J =1.5Hz=CH), 5.80 (1H, s, =CH), 5.99 (1H, brs, NH-Ph), 6.66-7.43 (5H, m, ArH),9.04 (1H, brs, CO - NH- CO), 10.04 (1H, brs, NH--NHPh).

Examples 2 to 7

In the same way as in Example 1, compounds expressed by the chemicalformulas shown below were prepared under the conditions shown in Table 1below. ##STR18##

                  TABLE 1                                                         ______________________________________                                                             Product                                                  Reaction Conditions    Yield   Melt point                                     Example                                                                              Temp (°C.)                                                                       Solvent  Time (h)                                                                             (%)   (°C.)                           ______________________________________                                        2      -10       ether    1      80    168-170                                3        5       benzene  1      46    173-174                                4      -10       THF      1.5    93    219-220                                5       40-45    THF      3      46    169-170                                6      Rm Temp.  THF      3      68    139-140                                7      Rm Temp   benzene  2      79    122 123                                ______________________________________                                    

Examples 8 and 9

The compounds obtained in Examples 1 and 2 were refluxed in a 10%solution of potassium hydroxide. The Example 1 compound was processedfor 4 hours and the Example 2 compound for 2 hours. The compoundsobtained respectively had melting points of 221° to 222° C (yield: 73%)and 254°to 255° C. (yield 52%).

These compounds had the following formulas: ##STR19##

The IR or ¹ H NMR data for the Example 8 and 9 compounds are as follows:

IR (KBr) 2548(OH), 1576 cm⁻¹ (C =N). ¹ H NMR (CDCl₃) δ=2.00 (3H, s,CH₃), 5.27, 5,33 (each 1H, s, =CH), 7.37 (5H, s, ArH), 8.83 (1H, s, OH).IR (KBr) 2588 (OH), 1578 cm.sup. =1 (C =N).

Examples 10 and 11

The compounds obtained in Examples 1 and 2 were refluxed in m-xyleneunder the conditions shown in Table 2. After cooling, the solvent wasdistilled away and each of the compounds was recrystallized from ethanolto give a product. The products were obtained in such yields and hadsuch melting points as shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Reaction Conditions                                                                              Product                                                    Example                                                                              Temperature                                                                              Time(h)  Yield (%)                                                                             Melt point (°C.)                    ______________________________________                                        10     Reflux     12       76      173-174                                    11     Reflux     12       22      187-188                                    ______________________________________                                    

It is presumed that these compounds have the following chemicalformulas. ##STR20##

Examples 12 to 14

Methacryloyl isocyanate was caused to react with each of the hydrazonecompounds expressed by the following formulas: ##STR21##

                  TABLE 3                                                         ______________________________________                                                             Product                                                  Reaction Conditions    Yield   Melt point                                     Example                                                                              Temp (°C.)                                                                       Solvent  Time (h)                                                                             (%)   (°C.)                           ______________________________________                                        12     -15--13   ether    2      86    144-145                                13     Rm Temp.  ether    5      57    117-118                                14     Reflux    THF      2      27    139-140                                ______________________________________                                    

The IR and ¹ H NMR data for the Example 12 compound are as follows:

IR (KBr) 3320, 3224 (NH), 1736 cm⁻¹ (C =0). ¹ H NMR (CDCl3) δ=1.70 (6H,s, N =C (CH₃)₂), 2.07 (3H, s, CH₃) 4.60 (1H, brs, =NH), 5.43 (2H, s,=CH), 6.90-7.50 (3H, m, ArH), 7.60-7.93 (2H, m, ArH).

The compound obtained was heated in a 10% acetic acid solution. Theresulting product had the following formula. ##STR22##

What is claimed is:
 1. A triazole compound represented by the formula(1)wherein R¹ represents a lower alkyl group which may have asubstituent selected from the group consisting of an alkyl group having1-6 carbon atoms; R² and R³ respectively hydrogen, an aryl group, having6-20 carbon atoms, a benzoyl group, a tosyl group, a lower alkoxycarbonyl group, or an aryl group having 6-20 carbon atoms andsubstituted with sulfonyl guoup, each of which except for hydrogen mayhave a substituent selected from the group consisting of methyl, ethyl,propylbutyl, 2-ethyl hexyl, methoxyethyl, ethoxyethyl, butoxyethyl,hexyloxyethyl, methoxy nitro, chloro and bromo provided that when R² ishydrogen, the triazole compound is represented by the formula (2):##STR23## wherein R¹ and R³ have the same as defined above.